WO2020218780A1 - Anode pour batterie secondaire au lithium et batterie secondaire au lithium la comprenant - Google Patents

Anode pour batterie secondaire au lithium et batterie secondaire au lithium la comprenant Download PDF

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WO2020218780A1
WO2020218780A1 PCT/KR2020/005152 KR2020005152W WO2020218780A1 WO 2020218780 A1 WO2020218780 A1 WO 2020218780A1 KR 2020005152 W KR2020005152 W KR 2020005152W WO 2020218780 A1 WO2020218780 A1 WO 2020218780A1
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layer
active material
negative electrode
lithium secondary
secondary battery
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PCT/KR2020/005152
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English (en)
Korean (ko)
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이진헌
김홍정
엄혜리
이상준
임대섭
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삼성에스디아이 주식회사
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Priority to US17/594,486 priority Critical patent/US20220263063A1/en
Priority to CN202080030569.6A priority patent/CN113711386A/zh
Priority to EP20796290.3A priority patent/EP3961759A4/fr
Priority to JP2021563109A priority patent/JP7246520B2/ja
Publication of WO2020218780A1 publication Critical patent/WO2020218780A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • It relates to a negative electrode for a lithium secondary battery and a lithium secondary battery including the same.
  • Lithium secondary batteries which have recently been in the spotlight as a power source for portable small electronic devices, use an organic electrolytic solution and thus exhibit a discharge voltage that is twice or more times higher than that of a battery using an aqueous alkaline solution, resulting in a high energy density.
  • the positive electrode active material of a lithium secondary battery is composed of lithium and a transition metal having a structure capable of intercalating lithium ions such as LiCoO 2 , LiMn 2 O 4 , and LiNi 1- x Co x O 2 (0 ⁇ x ⁇ 1). Oxide is mainly used.
  • the negative electrode active material various types of carbon-based materials including artificial, natural graphite, and hard carbon capable of inserting/detaching lithium have been applied, and in order to obtain higher capacity than recently, it has been applied to non-carbon-based negative electrode active materials based on silicon or tin. There is a research in progress.
  • One embodiment is to provide a negative electrode for a lithium secondary battery having excellent physical properties, for example, adhesion, and electrolyte impregnation properties.
  • Another embodiment is to provide a lithium secondary battery including the negative electrode.
  • One embodiment is a current collector; And a negative active material layer formed on the current collector and including a carbon-based negative active material, wherein the negative active material layer has a multilayer structure of three or more layers, and at least one of the negative active material layers is defined by the following formula (1).
  • a negative electrode for a lithium secondary battery which is an alignment layer having a degree of diversity (DD) of 19 or more, is provided.
  • I a is the sum of peak intensities that appear at non-planar angles when XRD is measured using a CuK ⁇ ray
  • I total is the sum of peak intensity at all angles when XRD is measured using CuK ⁇ rays
  • the active material layer may have a multilayer structure of 3 to 5 layers.
  • the negative active material layer having a multilayer structure of three or more layers includes an inner layer, a surface layer in contact with the current collector, and an intermediate layer, which is at least one layer positioned between the inner layer and the surface layer, wherein the surface layer has a DD value of 19 or more. It can be a layer.
  • the alignment layer may have a DD value of 19 to 60.
  • the peak intensity value may be a peak integral area value.
  • At least one of the negative active material layers may be an alignment layer having a DD value of 19 or more, and at least one layer may be a non-oriented layer having a DD value of less than 19.
  • the cathode may have a peak intensity ratio (I (002) /I (110) ) of 50 to 300 on the (002) plane to the peak intensity of the (110) plane when XRD is measured using a CuK ⁇ ray.
  • the alignment layer may have a peak intensity ratio (I (002) /I (110) ) of 10 to 200 on the (002) plane to the peak intensity of the (110) plane when XRD is measured using a CuK ⁇ ray.
  • the non-oriented layer may have a peak intensity ratio (I (002) /I (110) ) of 200 to 500 on the (002) plane to the peak intensity of the (110) plane when XRD is measured using CuK ⁇ rays.
  • the total thickness of the negative active material layer may be 100 ⁇ m to 1000 ⁇ m.
  • the second carbon-based negative active material may be artificial graphite or a mixture of artificial graphite and natural graphite.
  • the negative active material layer may further include a Si-based negative active material, a Sn-based negative active material, lithium vanadium oxide, or a combination thereof.
  • Another embodiment is the cathode; A positive electrode including a positive electrode active material; And it provides a lithium secondary battery containing an electrolyte.
  • the lithium secondary battery may be a high-power battery.
  • the negative electrode for a lithium secondary battery according to an embodiment may provide a lithium secondary battery having excellent battery characteristics.
  • FIG. 1 is a schematic diagram illustrating an orientation in an embodiment of the present invention.
  • FIG. 2 is a schematic view showing a structure of a cathode according to an embodiment of the present invention.
  • FIG. 3 is a schematic diagram of an orientation of a cathode according to an embodiment of the present invention.
  • FIG. 4 is a schematic view showing the structure of a rechargeable lithium battery according to an embodiment of the present invention.
  • the negative electrode for a lithium secondary battery includes a current collector and a negative electrode active material layer formed on the current collector and including a carbon-based negative active material, and the negative active material layer has a multilayer structure of three or more layers. , At least one of the negative active material layers is an alignment layer having a Degree of Divergence (DD) value of 19 or higher.
  • DD Degree of Divergence
  • the DD value is a value defined by Equation 1 below.
  • I a is the sum of peak intensities that appear at non-planar angles when XRD is measured using a CuK ⁇ ray
  • I total is the sum of peak intensity at all angles when XRD is measured using a CuK ⁇ ray.
  • graphite is classified into a hexagonal structure and a rhombohedral structure having an ABAB-type stacking sequence according to the stacking order of the graphene layer, and the R Surface means a lombohedral structure, and the H surface means a hexagonal structure.
  • a peak intensity value refers to a height value of a peak or an integral area value of a peak
  • a peak intensity value according to an embodiment refers to an integrated area value of a peak
  • the DD value is a value indicating that the negative active material included in the negative active material layer is oriented at a certain angle, and a larger value indicates that the negative active material is well oriented.
  • the larger the DD value the higher the angle (a) when the negative active material (3) is oriented with an angle (a) with respect to one side of the substrate (1). do.
  • this DD value is a value maintained even when charging and discharging proceeds.
  • the DD value may be 19 to 60, and may be 19 to 40.
  • the DD value of the alignment layer satisfies the above condition, it indicates that the negative active material included in the alignment layer, which is the negative active material layer, is oriented at an appropriate constant angle, and this value is a property value maintained even when charging and discharging proceeds. .
  • the negative active material is not in a state where it lies horizontally with the current collector, but is sufficiently aligned to facilitate the movement of Li ions within the negative electrode, that is, a constant angle with respect to the current collector
  • the (002) plane of graphite is arranged at an angle of more than 0 degrees (°) and less than 90 degrees (°), and therefore, the difficult orientation is controlled, and the DD value is less than 19
  • the direct current internal resistance may be increased, the rate characteristics, particularly the high rate characteristics may be markedly deteriorated, and the cycle life characteristics may be deteriorated, which is not appropriate.
  • the DD value is 19 or more and 60 or less, it does not mean that the negative active material is oriented substantially vertically with the current collector, and if it is oriented vertically, the battery is deformed as charging and discharging proceeds. Can cause problems.
  • the negative active material layer has a multilayer structure of three or more layers, and in one embodiment, may have a multilayer structure of three to five layers. In such a multilayer structure, at least one layer may be an alignment layer having the DD value of 19 or higher.
  • the negative electrode active material layer having a multilayer structure of three or more layers includes an inner layer, a surface layer in contact with the current collector, and an intermediate layer that is at least one layer positioned between the inner layer and the surface layer, and the surface layer has a DD value of 19 or more. It is appropriate that it is an alignment layer.
  • the cathode 30 is a structure in which a current collector 32, an inner layer 34, an intermediate layer 36, and a surface layer 38 are sequentially stacked, and in this case, the surface layer 38 ) Is an alignment layer having a DD value of 19 or higher.
  • the surface layer is an alignment layer, that is, when the anode active material orientation is high, the anode active material is not lying horizontally with respect to the current collector, but is standing at a certain angle, so that the electrolyte can be better impregnated into the anode active material layer,
  • a negative electrode can be more suitably applied to a high-power battery, and a battery having excellent high-rate characteristics can be provided.
  • the negative active material may be in a case where the negative active material is laid horizontally with respect to the current collector, if it is positioned vertically, etc. Impregnation property may be deteriorated, and the movement path of lithium ions becomes long, and thus, it cannot be effectively applied to a high-power battery.
  • At least one layer may be an alignment layer having a DD value of 19 or higher, and at least one layer may be a non-oriented layer having a DD value of less than 19.
  • the negative active material layer has a multilayer structure of three or more layers and includes both an oriented layer and a non-oriented layer, uniformity of reaction is ensured within the same layer, and binder migration is suppressed during drying.
  • a composite layer in the electrode plate (including an active material, a binder, and optionally a conductive material, and an active material layer formed on the current collector) It can have the advantage of reducing the electron resistance of (meaning), and has the effect of reducing the ionic resistance of the cathode.
  • the alignment portion and the non-alignment portion do not exist as separate layers, and if the alignment portion and the non-alignment portion exist together in one layer, the alignment portion/non-alignment portion Adhesion decreases due to binder migration during drying, increase in cathode ion resistance, and electrolyte impregnation properties vary depending on the oriented/non-oriented parts, resulting in increased reaction non-uniformity, and local thickness non-uniformity and high rate of 1C or more when full When charging with furnace, it is not suitable because there is a disadvantage of Li precipitation.
  • the negative electrode active material layer has a multilayer structure and has an oriented layer and a non-oriented layer
  • binder aggregation during drying during high-speed coating It is difficult to suppress migration, and thus there may be a disadvantage of increasing the ionic resistance and the electron resistance of the composite material layer in the electrode plate.
  • the negative active material layer is 3 or more, at least 3 to 5 layers, and the number of layers is 3 or 5, and when the number of layers is odd, the alignment layer is 1 layer, when the surface layer is 1 layer, There are 3 layers and 5 layers, and the non-oriented layer may be 2 layers and 4 layers.
  • the alignment layer may be 1 layer and 4 layers, and the non-alignment layer may be 2 layers and 3 layers.
  • the negative electrode When XRD is measured using a CuK ⁇ ray, the negative electrode may have a peak intensity ratio of the (002) plane to the peak intensity of the (110) plane, that is, I (002) /I (110) of 50 to 300.
  • I (002) /I (110) of the negative electrode When I (002) /I (110) of the negative electrode is included in the above range, there may be advantages of reducing internal resistance, improving high rate/lifetime characteristics, and reducing resistance of the composite layer in the electrode plate.
  • the alignment layer may have a peak intensity ratio (I (002) /I (110) ) of 10 to 200 on the (002) plane to the peak intensity of the (110) plane when XRD is measured using a CuK ⁇ ray.
  • I (002) / I (110) of the alignment layer is included in the above range, there is an advantage in that the DC internal resistance is not increased, in particular, high rate characteristics can be improved, and cycle life characteristics can be improved. I can.
  • the non-oriented layer may have a peak intensity ratio (I (002) /I (110) ) of 200 to 500 on the (002) plane to the peak intensity of the (110) plane when XRD is measured using CuK ⁇ rays.
  • I (002) /I (110) of the non-alignment layer is included in the above range, there may be an advantage in that the contact between the active material particles is improved and the resistance of the composite material in the electrode plate is reduced.
  • the DD value is a peak value that appears at non-planar angles with respect to the peaks appearing at all angles, so I (002) /I (110) and I (002) / I (110)
  • the number of 50 to 300 does not mean that the DD values of the first layer and the second layer according to the exemplary embodiment have the above range.
  • the total thickness of the negative active material layer may be 100 ⁇ m to 1000 ⁇ m.
  • the negative active material layer according to the exemplary embodiment may be formed to a maximum thickness of 1000 ⁇ m, which is much larger than the maximum thickness of 70 ⁇ m of a typical negative active material layer.
  • the negative electrode active material layer has a multilayer structure of three or more layers, and it is appropriate if the total thickness of all active material layers falls within the above range, and the thickness of each layer is not required to be limited.
  • the active material layer is formed in a multilayer structure of three or more layers, and at this time, the DD value of the surface layer is adjusted to 19 or more to improve the electrolyte impregnation, so that the thick layer is formed as such. Even so, high rate charging and discharging can be effectively performed, and thus, it can be usefully applied to high-power batteries.
  • the DD value is a value obtained by measuring XRD for a negative electrode obtained by disassembling a battery in a completely discharged state after charging and discharging a lithium secondary battery including the negative electrode. At this time, the charging and discharging conditions are performed once to twice at 0.1C to 0.2C .
  • the BET specific surface area of the negative electrode may be less than 5.0 m 2 /g, and may be 0.6 m 2 /g to 2.0 m 2 /g. If the BET specific surface area of the negative electrode is less than 5.0 m 2 /g, there may be an advantage that the electrochemical life characteristics of the cell may be improved.
  • the negative electrode obtained by disassembling the battery fully discharged to 3 V or less is cut into a predetermined size and placed in a BET sample holder. And measured by nitrogen gas adsorption method.
  • the negative electrode may have a cross-sectional loading level (L/L) of 6 mg/cm 2 to 65 mg/cm 2 .
  • the negative electrode active material may be artificial graphite or a mixture of artificial graphite and natural graphite.
  • artificial graphite or a crystalline carbon-based material that is a mixture of artificial graphite and natural graphite as the negative active material, the crystallographic properties of the particles are more developed than in the case of using an amorphous carbon-based active material. There may be an advantage of further improving the orientation characteristics of the carbon material.
  • the artificial graphite or natural graphite may be amorphous, plate-shaped, flake-shaped, spherical, fibrous, or a combination thereof, and any shape may be used.
  • the mixing ratio may be 70: 30% by weight to 95: 5% by weight.
  • the negative active material layer may further include at least one of a Si-based negative active material, an Sn-based negative active material, and a lithium vananium oxide negative active material.
  • the negative active material layer further includes these, that is, when the carbon-based negative active material is used as the first negative active material and the negative active material is used as the second negative active material, the mixing ratio of the first and second negative active materials is 50:50 to 99 : It may be 1 weight ratio.
  • the Si-based negative active material is Si, Si-C composite, SiO x (0 ⁇ x ⁇ 2), Si-Q alloy (where Q is an alkali metal, alkaline earth metal, group 13 element, group 14 element, group 15 element, 16 It is an element selected from the group consisting of group elements, transition metals, rare earth elements, and combinations thereof, and not Si), and the Sn-based negative active material is Sn, SnO 2 , Sn-R alloy (the R is an alkali metal, alkaline earth metal , An element selected from the group consisting of a group 13 element, a group 14 element, a group 15 element, a group 16 element, a transition metal, a rare earth element, and combinations thereof, and not Sn), and at least one of them And SiO 2 may be mixed and used.
  • the elements Q and R include Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Tl, Ge, P, As, Sb, Bi, What is selected from the group consisting of S, Se, Te, Po, and combinations thereof may be used.
  • the content of the negative active material in the negative active material layer may be 95% to 99% by weight based on the total weight of each layer, and as a result, may be 95% to 99% by weight based on the total weight of the negative active material layer.
  • the negative active material layer may include a binder, and may further include a conductive material.
  • the content of the binder in the negative active material layer may be 1% to 5% by weight based on the total weight of the negative active material layer.
  • the negative active material may be used in an amount of 90% to 98% by weight
  • a binder may be used in an amount of 1% to 5% by weight
  • a conductive material may be used in an amount of 1% to 5% by weight.
  • the binder serves to attach the negative active material particles well to each other and also to the negative active material to the current collector.
  • a non-aqueous binder, an aqueous binder, or a combination thereof may be used as the binder.
  • non-aqueous binder examples include ethylene propylene copolymer, polyacrylonitrile, polystyrene, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, Polyethylene, polypropylene, polyamideimide, polyimide, or combinations thereof.
  • aqueous binder examples include styrene-butadiene rubber, acrylated styrene-butadiene rubber (ABR), acrylonitrile-butadiene rubber, acrylic rubber, butyl rubber, polymer containing ethylene oxide, polyvinylpyrrolidone, and polyester.
  • ABR acrylated styrene-butadiene rubber
  • acrylonitrile-butadiene rubber acrylic rubber
  • butyl rubber polymer containing ethylene oxide
  • polyvinylpyrrolidone polyvinylpyrrolidone
  • polyester resin examples include styrene-butadiene rubber, acrylated styrene-butadiene rubber (ABR), acrylonitrile-butadiene rubber, acrylic rubber, butyl rubber, polymer containing ethylene oxide, polyvinylpyrrolidone, and polyester.
  • a cellulose-based compound capable of imparting viscosity may be further included as a thickener.
  • a cellulose-based compound capable of imparting viscosity may be further included as a thickener.
  • the cellulose-based compound one or more types of carboxymethyl cellulose, hydroxypropylmethyl cellulose, methyl cellulose, or alkali metal salts thereof may be mixed and used. Na, K, or Li may be used as the alkali metal.
  • the content of the thickener may be 0.1 to 3 parts by weight based on 100 parts by weight of the negative active material.
  • the conductive material is used to impart conductivity to the electrode, and in the battery to be constructed, any material may be used as long as it does not cause chemical change and is an electron conductive material.
  • the conductive material include carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, and carbon fiber; Metal-based materials such as metal powder or metal fibers such as copper, nickel, aluminum, and silver; Conductive polymers such as polyphenylene derivatives; Alternatively, a conductive material containing a mixture thereof may be used.
  • a copper foil, a nickel foil, a stainless steel foil, a titanium foil, a nickel foam, a copper foam, a polymer substrate coated with a conductive metal, and a combination thereof may be used.
  • the negative electrode according to this exemplary embodiment may be formed by applying a magnetic field when the negative active material composition is applied to a current collector.
  • a negative electrode manufacturing process according to an embodiment, for example, a case where the negative active material layer is three layers, will be described in detail below with reference to FIG. 3.
  • the first layer composition including a negative active material is coated on the current collector. After coating the first layer composition, it is dried to form the first layer U1. Subsequently, the first layer is coated with a second layer composition including a negative active material, dried to form a second layer (U2), and a third layer composition including a negative active material is coated on the second layer. , Dried to form a third layer (U3).
  • the negative active material 3 included in the third layer U3 is an alignment layer oriented at a certain angle with the current collector, and FIG. 3 shows that the negative active material 3 is oriented on the third layer U3. As shown, this is an important element in that the third layer U3, which is the surface layer, is the alignment layer in the negative electrode according to the exemplary embodiment, so it only shows that the negative active material 3 included in the third layer U3 is oriented. , The orientation states of the negative active materials included in the first and second layers are not shown.
  • the strength of the magnetic field by the magnet may be 1000 Gauss to 10000 Gauss.
  • the negative active material composition after the negative active material composition is applied to the current collector, it may be maintained for 3 seconds to 9 seconds, that is, exposed to the magnetic field for 3 seconds to 9 seconds.
  • the magnetic flux by the magnet is formed in a direction perpendicular to the current collector, but the coating speed (the current collector moving speed) Accordingly, the direction in which the magnetic field is formed is formed with a certain angle as a vector function, so that the negative electrode active material included in the first layer and the second composition stands at a certain angle with respect to the surface of the current collector, that is, is oriented. It can take shape.
  • the magnetic flux by the magnet is formed in a direction perpendicular to the current collector, but the direction in which the magnetic field is formed depending on the coating speed (the current collector moving speed). Since silver is formed with a constant angle as a vector function, the negative active material included in the negative active material composition may stand at a certain angle with respect to the surface of the current collector, that is, may have a shape that is oriented.
  • the DD value may be formed differently. That is, when forming a multilayer structure of three or more layers, it is appropriate to form each layer by adjusting the viscosity of the composition for forming the layer so that the layer to be produced can be an oriented layer or a non-oriented layer.
  • the viscosity of the composition In order for the layer to be formed to become an alignment layer, the viscosity of the composition must be at least 2000 cps and less than 4000 cps at room temperature (about 20° C. to about 25° C.), and the viscosity of the composition must be at room temperature (about 20° C. to about 25° C.). °C) should be between 4000cps and 5000cps. Particularly, when the viscosity of the composition is contained in 2000 cps or more and less than 4000 cps at room temperature (about 20° C. to about 25° C.), the DD value of the formed layer is 19 or more, and specifically, the viscosity of the composition is at room temperature (about 20° C. °C to about 25 °C), 2000 cps to 3500 cps, the DD value of the formed layer may be 19 to 60 oriented layer.
  • a non-oriented layer having a DD value of less than 19 may be formed.
  • the composition may be prepared by mixing a negative active material, a binder, and a conductive material in a solvent.
  • the negative active material, the binder, and the conductive material are as described above.
  • the solvent may be an organic solvent such as N-methylpyrrolidone or water, and when an aqueous binder is used as the binder, water may be used as the solvent.
  • a lithium secondary battery includes the negative electrode, a positive electrode, and an electrolyte.
  • the lithium secondary battery may be a high-power battery. That is, it can be usefully used in electronic devices that require high output, such as power tools, automobiles, and vacuum cleaners.
  • the lithium secondary battery including the negative electrode according to the embodiment can easily discharge heat generated during charging and discharging, particularly heat generated by charging and discharging when used in high-capacity cells and high-power electronic devices. Since the resulting battery deterioration can be suppressed, it can be effectively used as a high-power battery. In addition, heat due to charging and discharging can be easily released, so that an increase in battery temperature can be effectively suppressed, and cycle life characteristics, particularly, cycle life characteristics at a high rate can be effectively improved.
  • Such a high-power battery may be a cylindrical battery, a pouch-type battery, or a stack type battery.
  • a cylindrical battery may be a battery of a large standard such as an 18650 type battery (diameter 18 mm, height 65 mm), a 21700 type battery (diameter 21 mm, height 70 mm).
  • the positive electrode includes a current collector and a positive electrode active material layer formed on the current collector.
  • a compound capable of reversible intercalation and deintercalation of lithium (reitiated intercalation compound) may be used.
  • a composite oxide of lithium and a metal selected from cobalt, manganese, nickel, and combinations thereof may be used.
  • a compound represented by any one of the following formulas may be used.
  • Li a A 1-b X b D 2 (0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5); Li a A 1-b X b O 2-c D c (0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05); Li a E 1-b X b O 2-c D c (0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05); Li a E 2-b X b O 4-c D c (0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05); Li a Ni 1-bc Co b X c D ⁇ (0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.5, 0 ⁇ ⁇ 2); Li a Ni 1-bc Co b X c O 2- ⁇ T ⁇ (0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇
  • A is selected from the group consisting of Ni, Co, Mn, and combinations thereof;
  • X is selected from the group consisting of Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements, and combinations thereof;
  • D is selected from the group consisting of O, F, S, P, and combinations thereof;
  • E is selected from the group consisting of Co, Mn, and combinations thereof;
  • T is selected from the group consisting of F, S, P, and combinations thereof;
  • G is selected from the group consisting of Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, and combinations thereof;
  • Q is selected from the group consisting of Ti, Mo, Mn, and combinations thereof;
  • Z is selected from the group consisting of Cr, V, Fe, Sc, Y, and combinations thereof;
  • J is selected from the group consisting of V, Cr, Mn, Co, Ni, Cu, and combinations thereof.
  • This coating layer contains at least one coating element compound selected from the group consisting of oxides of coating elements, hydroxides of coating elements, oxyhydroxides of coating elements, oxycarbonates of coating elements, and hydroxycarbonates of coating elements. I can.
  • the compound constituting these coating layers may be amorphous or crystalline.
  • As a coating element included in the coating layer Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or a mixture thereof may be used.
  • the coating layer formation process may be any coating method as long as the compound can be coated by a method that does not adversely affect the physical properties of the positive electrode active material by using these elements (e.g. spray coating, dipping method, etc.). Since the content can be well understood by those engaged in the relevant field, detailed description will be omitted.
  • the content of the positive electrode active material may be 90% to 98% by weight based on the total weight of the positive electrode active material layer.
  • the positive active material layer may further include a binder and a conductive material.
  • the content of the binder and the conductive material may be 1% to 5% by weight, respectively, based on the total weight of the positive electrode active material layer.
  • the binder serves to attach the positive electrode active material particles well to each other, and to attach the positive electrode active material to the current collector well.
  • Representative examples of the binder include polyvinyl alcohol, carboxymethylcellulose, hydroxypropylcellulose, diacetylcellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymer containing ethylene oxide, polyvinylpyrroly. Don, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene butadiene rubber, acrylated styrene butadiene rubber, epoxy resin, nylon, and the like may be used, but are not limited thereto.
  • the conductive material is used to impart conductivity to the electrode, and in the battery to be constructed, any material may be used as long as it does not cause chemical change and is an electron conductive material.
  • the conductive material include carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, and carbon fiber; Metal-based materials such as metal powder or metal fibers such as copper, nickel, aluminum, and silver; Conductive polymers such as polyphenylene derivatives; Alternatively, a conductive material containing a mixture thereof may be mentioned.
  • Al may be used as the current collector, but is not limited thereto.
  • the electrolyte includes a non-aqueous organic solvent and a lithium salt.
  • the non-aqueous organic solvent serves as a medium through which ions involved in the electrochemical reaction of a battery can move.
  • non-aqueous organic solvent a carbonate-based, ester-based, ether-based, ketone-based, alcohol-based, or aprotic solvent may be used.
  • the carbonate-based solvents include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), ethylene carbonate ( EC), propylene carbonate (PC), butylene carbonate (BC), and the like may be used.
  • Examples of the ester solvent include methyl acetate, ethyl acetate, n-propyl acetate, t-butyl acetate, methyl propionate, ethyl propionate, decanolide, mevalonolactone, and caprolactone ( caprolactone) and the like may be used.
  • ether solvent dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, and the like may be used.
  • cyclohexanone or the like may be used as the ketone solvent.
  • R-CN R is a linear, branched, or cyclic hydrocarbon group having 2 to 20 carbon atoms
  • a double bonded aromatic ring or an ether bond such as nitriles, amides such as dimethylformamide, dioxolanes such as 1,3-dioxolane, sulfolanes, etc. may be used. .
  • the organic solvent may be used alone or as a mixture of one or more, and the mixing ratio in the case of using one or more mixtures may be appropriately adjusted according to the desired battery performance, which may be widely understood by those engaged in the field. have.
  • the electrolyte may exhibit excellent performance.
  • the organic solvent may further include an aromatic hydrocarbon-based organic solvent in the carbonate-based solvent.
  • the carbonate-based solvent and the aromatic hydrocarbon-based organic solvent may be mixed in a volume ratio of 1:1 to 30:1.
  • an aromatic hydrocarbon-based compound of Formula 1 may be used as the aromatic hydrocarbon-based organic solvent.
  • R 1 to R 6 are the same or different from each other and are selected from the group consisting of hydrogen, halogen, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group, and combinations thereof.
  • aromatic hydrocarbon-based organic solvent examples include benzene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3-tri Fluorobenzene, 1,2,4-trifluorobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1 ,2,4-trichlorobenzene, iodobenzene, 1,2-diaiodobenzene, 1,3-diaiodobenzene, 1,4-diaiodobenzene, 1,2,3-triiodobenzene, 1, 2,4-triiodobenzene, toluene, fluorotoluene, 2,3-difluorotoluene, 2,4--t
  • the electrolyte may further include vinylene carbonate or an ethylene carbonate-based compound of Formula 2 as a life-improving additive in order to improve battery life.
  • R 7 and R 8 are the same as or different from each other, and are selected from the group consisting of hydrogen, a halogen group, a cyano group (CN), a nitro group (NO 2 ), and a fluorinated alkyl group having 1 to 5 carbon atoms.
  • At least one of R 7 and R 8 is selected from the group consisting of a halogen group, a cyano group (CN), a nitro group (NO 2 ), and a fluorinated alkyl group having 1 to 5 carbon atoms, provided that both R 7 and R 8 Not hydrogen.
  • ethylene carbonate-based compound examples include difluoro ethylene carbonate, chloroethylene carbonate, dichloroethylene carbonate, bromoethylene carbonate, dibromoethylene carbonate, nitroethylene carbonate, cyanoethylene carbonate or fluoroethylene carbonate. I can. When further use of such a life-improving additive is used, the amount of the additive may be appropriately adjusted.
  • the lithium salt is a material that is dissolved in an organic solvent and acts as a source of lithium ions in the battery, enabling the operation of a basic lithium secondary battery, and promoting movement of lithium ions between the positive electrode and the negative electrode.
  • Representative examples of such lithium salts are LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiN(SO 2 C 2 F 5 ) 2 , Li(CF 3 SO 2 ) 2 N, Li(FSO 2 ) 2 N (lithium bisfluoro Rosulfonylimide (lithium bis(fluorosulfonyl)imide: LiFSI), LiN(SO 3 C 2 F 5 ) 2 , LiC 4 F 9 SO 3 , LiClO 4 , LiAlO 2 , LiAlCl 4 , LiN(C x F 2x+ 1 SO 2 )(C y F 2y+1 SO 2 ) (where x and y are natural numbers, for example, integers of 1 to 20),
  • the concentration of the lithium salt is preferably used within the range of 0.1 M to 2.0 M.
  • the concentration of the lithium salt is within the above range.
  • a separator may exist between the positive electrode and the negative electrode.
  • Polyethylene, polypropylene, polyvinylidene fluoride, or a multilayer film of two or more layers thereof may be used as such a separator, and a polyethylene/polypropylene two-layer separator, a polyethylene/polypropylene/polyethylene three-layer separator, a polypropylene/polyethylene/poly It goes without saying that a mixed multilayer film such as a three-layer propylene separator may be used.
  • a lithium secondary battery according to an embodiment may be a cylindrical battery.
  • the rechargeable lithium battery 100 has a cylindrical shape, a negative electrode 112, a positive electrode 114, a separator 113 disposed between the negative electrode 112 and the positive electrode 114, and the negative electrode 112. , An electrolyte (not shown) impregnated in the positive electrode 114 and the separator 113, a battery container 120, and a sealing member 140 for sealing the battery container 120 as main parts.
  • the lithium secondary battery 100 is configured by sequentially stacking the negative electrode 112, the positive electrode 114, and the separator 113, and then receiving them in the battery container 120 while being wound in a spiral shape.
  • Example 1 3-layer structure, 1 layer and surface layer (3 layers) are alignment layers
  • anode active material slurry for the first layer having a viscosity (at 25°C) of 3000 cps.
  • the negative active material slurry for the first layer was applied to the Cu foil, exposed to the magnetic field for 9 seconds, and dried.
  • a first layer having a thickness of 40 ⁇ m was formed.
  • the negative active material slurry for the second layer is applied to the first layer, exposed to a magnetic field for 9 seconds, and then dried to form a second layer having a thickness of 40 ⁇ m, and the third layer is formed on the second layer.
  • a negative active material slurry for a layer was applied, exposed to a magnetic field for 9 seconds, and dried to form a third layer having a thickness of 50 ⁇ m.
  • a rolling process was performed to prepare a negative electrode having a cross-sectional loading level (L/L) of 15 mg/cm 2 .
  • a cathode active material slurry was prepared by mixing 96% by weight of a LiCoO 2 positive electrode active material, 2% by weight of a carbon black conductive agent, and 2% by weight of a polyvinylidene fluoride binder in an N-methylpyrrolidone solvent. The prepared slurry was applied to an Al substrate, dried, and rolled to prepare a positive electrode.
  • Example 2 4 layer structure, 1 layer and surface layer (4 layers) are alignment layers
  • anode active material slurry for the first layer having a viscosity (at 25°C) of 3000 cps.
  • the negative active material slurry for the first layer was applied to the Cu foil, exposed to the magnetic field for 9 seconds, and dried.
  • a first layer having a thickness of 30 ⁇ m was formed.
  • the negative active material slurry for the second layer is applied to the first layer, exposed to a magnetic field for 9 seconds, and then dried to form a second layer having a thickness of 30 ⁇ m, and the third layer is formed on the second layer.
  • the negative active material slurry for a layer was applied, exposed to a magnetic field for 9 seconds, and dried to form a third layer having a thickness of 30 ⁇ m, and the negative active material slurry for the fourth layer was applied to the third layer, followed by 9 seconds. After being exposed to a magnetic field for a while, it was dried to form a fourth layer having a thickness of 40 ⁇ m.
  • a rolling process was performed to prepare a negative electrode having a cross-sectional loading level (L/L) of 15 mg/cm 2 .
  • a lithium secondary battery was manufactured in the same manner as in Example 1, except that the negative electrode was used.
  • Example 3 5-layer structure, 1 layer, 3 layers and surface layer (5 layers) are alignment layers
  • anode active material slurry for the first layer having a viscosity (at 25°C) of 3000 cps.
  • the negative active material slurry for the first layer was applied to the Cu foil, exposed to the magnetic field for 9 seconds, and dried.
  • a first layer having a thickness of 30 ⁇ m was formed.
  • the negative active material slurry for the second layer is applied to the first layer, exposed to a magnetic field for 9 seconds, and then dried to form a second layer having a thickness of 30 ⁇ m, and the third layer is formed on the second layer.
  • the negative active material slurry for a layer was applied, exposed to a magnetic field for 9 seconds, and dried to form a third layer having a thickness of 30 ⁇ m, and the negative active material slurry for the fourth layer was applied to the third layer, followed by 9 seconds.
  • a rolling process was performed to prepare a negative electrode having a cross-sectional loading level (L/L) of 15 mg/cm 2 .
  • a lithium secondary battery was manufactured in the same manner as in Example 1, except that the negative electrode was used.
  • the negative active material slurry for the first layer was applied to the Cu foil, exposed to the magnetic field for 3 seconds, and dried.
  • a first layer having a thickness of 60 ⁇ m was formed.
  • the negative active material slurry for the second layer was applied to the first layer, exposed to a magnetic field for 9 seconds, and dried to form a second layer having a thickness of 70 ⁇ m.
  • a rolling process was performed to prepare a negative electrode having a cross-sectional loading level (L/L) of 15 mg/cm 2 .
  • a lithium secondary battery was manufactured in the same manner as in Example 1, except that the negative electrode was used.
  • anode active material slurry having a viscosity (at 25°C) of 3000 cps.
  • the negative active material on the Cu foil After fixing two magnets with a magnetic field strength of 4000 Gauss at regular intervals in the width direction of the electrode plate, after placing the Cu foil in the upper direction of the magnet, while moving the Cu foil, the negative active material on the Cu foil The slurry was applied, exposed to a magnetic field for 9 seconds, and then dried to form a coating layer having a thickness of 130 ⁇ m.
  • the formed coating layer was positioned directly on the magnet, so that the part affected by the magnetic field was formed as an orientation part, and the part that was not affected by the magnetic field was formed as a non-oriented part because it was not located on the magnet, and was located between two magnets, that is, between the magnet and the magnet. .
  • a rolling process was performed to prepare a negative electrode having a cross-sectional loading level (L/L) of 15 mg/cm 2 .
  • a lithium secondary battery was manufactured in the same manner as in Example 1, except that the negative electrode was used.
  • the lithium secondary battery batteries prepared according to Examples 1 to 3 and Comparative Examples 1 to 2 were charged and discharged twice at 0.1C, and then completely discharged to 2.75V at 0.1C. This completely discharged battery was disassembled to obtain a negative electrode.
  • the sum of the integrated areas of the peaks appearing at ° ((004) plane) and 77.5 ⁇ 0.2° ((110) plane) was taken as I total , and DD(I total
  • I (002) / I (110) was calculated and shown in Table 2 below. In particular, at 43.4 ⁇ 0.2°, the peaks corresponding to the (101) R plane of graphite and the (111) plane of the Cu current collector were overlapped.
  • the DD of the negative electrodes prepared according to Examples 1 to 3 is 28.9 to 31.1
  • the first and third layers of Example 1 the first and fourth layers of Example 2, and , DD of the first layer, the third layer, and the fifth layer of Example 3 are included in the range of 19 to 60, and it can be seen that this is an alignment layer.
  • the peak intensity ratio of the negative electrode (I (002) /I (110) ) is included in the range of 50 to 300, and the peak intensity ratio of the alignment layer (I (002) /I (110) ) It can be seen that is included in the range of 10 to 200.
  • Examples 1 to 3 in which the surface layer is an alignment layer and three or more active material layers have very excellent high rate charge/discharge characteristics.
  • the alignment layer is included, it can be seen that the high rate charge/discharge life is deteriorated in the case of Comparative Example 1, which is a two-layer configuration, and Comparative Example 2 formed on one layer, where the alignment layer and the non-orientation layer are not separate layers have.
  • the battery was disassembled to obtain a negative electrode. After taking a sample having a size of 5 cm X 5 cm from the obtained negative electrode, the sample was cut into 0.5 cm X 0.5 cm and put in a BET sample holder, and BET was measured by a nitrogen gas adsorption method, and the results are shown in Table 4 below.
  • the on-batteries according to Examples 1 to 3 and Comparative Examples 1 to 2 were charged with a constant current and constant voltage under conditions of 1.0C, 4.4V, and 0.1C cut-off, and paused for 5 minutes, and then cut at 1.0C and 3.0V.
  • the constant current discharge was performed under the -off condition, and the condition of rest for 5 minutes was referred to as one charge/discharge cycle, and a total of 300 charge/discharge was performed.
  • the capacity retention rate according to this charge/discharge cycle was calculated as the ratio of the discharge capacity in each cycle to the one discharge capacity.
  • the active material layer is two layers (Comparative Example 1), or It can be seen that compared to the case where the orientation portion is formed as a single layer (Comparative Example 2), it exhibits excellent cycle life characteristics.

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Abstract

La présente invention concerne une anode pour une batterie secondaire au lithium et une batterie secondaire au lithium la comprenant. L'anode pour une batterie secondaire au lithium comprend un collecteur de courant et une couche de matériau actif d'anode formée sur le collecteur de courant et comprenant un matériau actif d'anode à base de carbone, la couche de matériau actif d'anode ayant une structure multicouche constituée d'au moins trois couches et au moins une couche des couches de matériau actif d'anode étant une couche orientée ayant un degré de divergence (DD) supérieur ou égal à 19, le DD étant défini par la formule suivante : [Formule 1] Degré de divergence (DD) = (Ia/Itotal)×100 (dans la formule 1, Ia est la somme des intensités de pics représentés à des angles non plan tel que mesuré par XRD au moyen d'un rayonnement CuKα, et Itotal est la somme des intensités des pics représentés à tous les angles tel que mesuré par XRD au moyen d'un rayonnement CuKα.)
PCT/KR2020/005152 2019-04-24 2020-04-17 Anode pour batterie secondaire au lithium et batterie secondaire au lithium la comprenant WO2020218780A1 (fr)

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CN202080030569.6A CN113711386A (zh) 2019-04-24 2020-04-17 用于锂二次电池的负极和包括该负极的锂二次电池
EP20796290.3A EP3961759A4 (fr) 2019-04-24 2020-04-17 Anode pour batterie secondaire au lithium et batterie secondaire au lithium la comprenant
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US20210408546A1 (en) * 2020-06-26 2021-12-30 Sk Innovation Co., Ltd. Anode for Lithium Secondary Battery and Lithium Secondary Battery Including the Same
EP4080604A3 (fr) * 2021-04-23 2022-11-02 Samsung SDI Co., Ltd. Électrode négative pour batterie rechargeable au lithium et batterie rechargeable au lithium la comprenant
WO2022237691A1 (fr) * 2021-05-08 2022-11-17 江苏正力新能电池技术有限公司 Pièce polaire d'électrode et batterie contenant une pièce polaire d'électrode

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EP4080604A3 (fr) * 2021-04-23 2022-11-02 Samsung SDI Co., Ltd. Électrode négative pour batterie rechargeable au lithium et batterie rechargeable au lithium la comprenant
WO2022237691A1 (fr) * 2021-05-08 2022-11-17 江苏正力新能电池技术有限公司 Pièce polaire d'électrode et batterie contenant une pièce polaire d'électrode

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